有机化合物水中溶解度的测定与估算

本文介绍用摇瓶法、产生柱法和动态联柱高效液相色谱法等方法测定有机化合物在水中溶解度的研究方法,同时给出了某些农药、硝基多环芳烃和氯苯类化合物的水中溶解度的实验数值.     

单甲脒水中溶解度及正辛醇／水分配系数的测定

有毒有机化合物在水中的溶解度(WS)及正辛醇/水分配系数(K_(ow)),是描述其在环境中行为的两个重要物理化学参数。本文用溶解度平衡曲线法和振荡法,测得单甲脒在水中的溶解度为21.8±1.3mg/1(25℃),其在正辛醇/水中的分配系数lgK_(ow)为2.92±0.06。     

部分PCDDF水溶解度的定量结构-性质关系

以量子化学PM3算法计算得到的12个量子化学参数作为分子结构描述符，运用偏最小二乘分析，首次建立23种PCDD/F水溶解度（logSw)的定量结构-性质关系模型。PCDD/F的Sw随着其分子量的增大而减少；随着其分子最低未占据轨道能（Eluno)的增大而增大，推测PCDD/F分子与水分子之间存在着电荷转移相互作用。     

有机酸碱类污染物溶解度的测定及估算

采用反相高效液相色谱法和振荡法测定了四十二种有机酸、碱化合物的溶解度,建立了用分配系数、熔点估算溶解度的方程,测定和估算了有机酸、碱类污染物在不同pH条件下的溶解度。实验测定值、文献值和估算值三者吻合较好。     

芳烃混合物溶解规律的研究

本文利用双波长紫外分光光度法测定了多种组成的芳烃混合物在水相的溶解度,发现有机相中共存物质的组成及相互作用对它们各自的水溶解度具有重要影响。实验表明:液-液混合物表现出接近理想溶液的溶解行为;固-固混合物的溶解行为比较复杂,结构相近的固-固混合物的溶解行为接近理想溶液,而结构不相近的固-固混合物中各组份的溶解度与纯物质的溶解度接近;完全相溶的液-固混合物经固/液逸度比校正后,表现出接近理想溶液的溶解行为,本文还利用UNIFAC官能团法估算了芳烃混合物的溶解度,理论预测和实验值吻合很好。     

取代氮杂环类有机物水溶解度的估算与测定

本文采用一种修正的分子连接性指数研究了氮杂环类化合物水溶解度的定量结构性性质关系，这种修正的分子连接性指数是由原子半么取代原子的点价计算得来。逐步多元统计回归表明氮杂环的水溶解度和２阶及５阶原子半么分子连接性指数呈良好的相关性。     

NaCl在Zn(Ⅱ)-NaOH-H_2O体系中溶解度的测定及去除

等温溶解平衡法测定了283.2～323.2 K温度范围内NaCl在Zn(Ⅱ)-NaOH-H2O体系(cZn(Ⅱ)=0.6 mol/L、cNaOH=5.00mol/L)及NaOH-H2O体系(cNaOH=5.00 mol/L)中的溶解度。与NaOH-H2O、纯水体系相比,相同温度下NaCl在Zn(Ⅱ)-NaOH-H2O体系中溶解度最小。运用正交实验法对Zn(Ⅱ)-NaOH-H2O体系中NaCl的溶解度进行因素分析。结果表明,较高的cNaOH和cZn(Ⅱ)是造成NaCl溶解度急剧降低的主要原因,提高温度虽然对NaCl的溶解有促进作用但影响较小。最后,通过加热浓缩方式提高溶液NaOH和Zn的浓度,促使NaCl因溶解度骤降而结晶析出,首次实现了碱锌溶液中高浓度Cl-的大量去除。实验结果具有重要的工程应用价值。     

The role of soil humic and fulvic acid in the sorption of endosulfan (alpha and beta)

The sorption behaviour of alpha- and beta-endosulfan in soil organic matter was investigated using standard soil humic acid (HA) and soil fulvic acid (FA) with a modified solubility enhancement method and a dialysis bag technique. For HA, all the experiments were conducted at an ionic strength of 0.001 mol/L, in both the presence and absence of calcium and at an ionic strength of 0.01 mol/L. For FA, the experiments were conducted at two ionic strengths: 0.001 mol/L (with calcium) and 0.01 mol/L. This study is the first to describe the striking differences in the sorption behaviours of the two stereoisomers of endosulfan in HA and in FA. The sorption coefficients of alpha-endosulfan in HA and FA were significantly higher than those of beta-endosulfan. Beta-endosulfan has comparable sorption coefficients (1.5–5.4 L/g) in HA and in FA. Ionic strength and the presence of calcium have no significant effect on the sorption of beta-endosulfan in HA. However, calcium can significantly (p=0.01) enhance the solubility of alpha-endosulfan in HA. Changes in ionic strength by one order of magnitude also affect the solubility of alpha-endosulfan in HA. The sorption coefficients of alpha-endosulfan in HA (10–36 L/g) were greater than those in FA (9–14 L/g). The chirality of the alpha-isomer was hypothesised to be the primary reason behind its higher sorption in soil organic matter relative to the beta-isomer. In the presence of dissolved HA and FA found in natural soil environments, solubility of endosulfan can be increased by five times than the aqueous solubility of endosulfan without HA and FA.     

Properties of Starch/PVA Blend Films Containing Citric Acid as Additive

Starch/polyvinyl alcohol (PVA) blend films were prepared successfully by using starch, polyvinyl alcohol (PVA), glycerol (GL) sorbitol (SO) and citric acid (CA) for the mixing process. The influence of mixing time, additional materials and drying temperature of films on the properties of the films was investigated. With increase in mixing time, the tensile strength (TS), elongation (%E), degree of swelling (DS) and solubility (S) of the film were equilibrated. The equilibrium for TS, %E, DS and S value was 20.12 MPa, 36.98%, 2.4 and 0.19, respectively. The mixing time of equilibrium was 50 min. TS, %E, DS and S of starch/PVA blend film were examined adding glycerol (GL), sorbitol (SO) and citric acid (CA) as additives. At all measurement results, except for DS, the film adding CA was better than GL or SO because hydrogen bonding at the presence of CA with hydroxyl group and carboxyl group increased the inter/intramolecular interaction between starch, PVA and additives. Citric acid improves the properties of starch/PVA blend film compared to glycerol and sobitol. When the film was dried at low temperature, the properties of the films were clearly improved because the hydrogen bonding was activated at low temperature.     

针铁矿对硫酸盐还原菌分解铅矾的影响

铅矾(PbSO_4)是工业生产中释放进入环境的重要含Pb物相,具有潜在的环境风险.采用硫酸盐还原菌(SRB)在厌氧条件下将重金属沉淀形成低溶度积的硫化物是有效固定重金属的方法之一.本研究重点考察了SRB作用下铅矾的转化过程及针铁矿对铅矾分解的影响.结果表明,反应体系中溶液p H和ORP均有所降低;SO_4~(2-)在SRB生长停滞期上升,随后保持稳定;酸可挥发性S浓度随SRB的生长逐渐升高,并最后保持稳定;实验结束后铅矾大部分转化为白铅矿(PbCO_3)和方铅矿.对结果的分析表明,在SRB作用下,铅矾分解转化的机制为:首先转化为白铅矿,其次硫酸盐被还原产生S~(2-),进一步促进铅矾的分解和白铅矿的形成,最后S~(2-)同溶液及新生白铅矿中的Pb~(2+)反应生成溶度积更低的方铅矿;针铁矿的主要作用为:固定溶液中的S~(2-),降低铅矾SRB分解的环境污染风险;通过作为SRB生长的电子受体和降低S~(2-)的生物毒害作用,提高体系中SRB的生物活性.